Polymers containing an acetoacetate moiety

ABSTRACT

The present invention provides polymers containing an acetoacetate moiety. The polymers may be readily functionalized and the functionalized polymers may be further derivatized to provide a wide variety of useful polymers having desirable chemical and physical properties. The polymers of the present invention may be employed in a wide variety of compositions, wherein R 1 -R 6 , w, y, and z are described herein.

FIELD OF THE INVENTION

The present invention provides polymers containing an acetoacetatemoiety. The polymers may be readily functionalized and thefunctionalized polymers may be further derivatized to provide a widevariety of useful polymers having desirable chemical and physicalproperties. The polymers of the present invention may be employed in awide variety of compositions.

BACKGROUND OF THE INVENTION

Inkjet printers form an image by firing a plurality of discrete drops ofink from one or more nozzles on to the surface of a recording sheetplaced adjacent the nozzles. Modern inkjet printers can print on almostany conventional paper or similar medium. The quality of images producedby such printers is greatly affected by the properties of the mediumused. More particularly, to produce high quality images reliably, it isnecessary that the recording medium, i.e., the inkjet recording sheet,dry rapidly, exhibit good ink adhesion, resist image cracking, notpromote excessive spreading of the ink droplet, not promote “wicking”,that is spreading of ink by capillary action through fibrous medium suchas paper, and, importantly, be such that the contrast of the dried imagewith moist surfaces does not result in bleeding of ink from the image.Printing technologies are applied to many different surfaces, forexample, polyester film, polyolefin films including polyethylene (PE),polypropylene (PP), polycarbonate, polyimide films, metals (i.e.,aluminum, steel, copper), glass, vinyl film, Tyvek, canvas,polyvinylidene chloride films, textiles, canvas, leather, rubber, paper,polyurethane, ceramics, wood and the like.

In curable ink systems, the inks can be prepared by a polymerizationprocess initiated by thermal or photo irradiation (α, γ, and x-rays, UV,E-beam, and the like). Desirable properties in polymeric inks includesolution viscosity, lubricity, gloss, cure speed, adhesion, impactresistance, toughness, coating hardness, water resistance, tack, surfacetension, wetting, foaming, tensile strength, solvency, dispersiveproperties, flexibility, chemical resistance, abrasion resistance, andpenetration.

The functional attributes of acetoacetoxyethyl methacrylate aredisclosed in Eastman Chemical's “Acetoacetoxyethyl methacrylate (AAEM)Acetoacetyl Chemistry” Brochure (Publication Number N-319C, December1999), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of diketene chemistry are disclosedin “Diketene” by R. Clemens (Chemical Reviews, Volume 86, Number 2,April 1986), which disclosure is incorporated by reference herein. Thefunctional and chemical attributes of ketene chemistry are disclosed in“Ketenes II” by T. Tidwell (J. Wiley and Sons, New Jersey, USA, 2006),which disclosure is incorporated by reference herein.

EP 1578824B1 describes a curable liquid composition containing anacryloyl group containing resin produced by reacting monofunctionalvinyl compounds and multifunctional acrylic esters with β-dicarbonylgroup containing compound in which the two activated hydrogen atoms arein its methylene position. Self-initiating photocurable resins thatUV-cure with little or no photoinitiator are described in Michael L.Gould et al., Novel Self-Initiating UV-Curable Resins: Generation Three,1 PROCEEDINGS FROM RADTECH EUROPE 05, 245-51 (2005). These disclosuresare incorporated by reference herein.

U.S. 2010/0041846 discloses lactam/vinyl alcohol copolymers,specifically, hydrophobic cross-linkable) acetylated lactam/vinylalcohol copolymers. U.S. Pat. No. 6,933,024 discloses the use andpreparation of poly(vinylpyrrolidone-(PVP) co-vinylalcohol) as an inkjetrecording material by hydrolyzing PVP/polyvinylacetate copolymer. U.S.Pat. No. 4,350,788 describes a synthetic resin emulsion containing anacetoacetylated polyvinyl alcohol. U.S. Pat. No. 2,536,980 describessynthetic polyvinyl alcohol-1-butene-1,3-diones. U.S. Pat. No. 5,227,423describes latex paint comprised of polymers having anon-self-polymerizable monomer, such as maleic acid and itaconic acid, aco-polymerizable monomer, such as a N-vinyl lactam, an acrylate, such as2-hydroxyethyl acrylate, a wet adhesion promoting monomer, such asacetoacetoxyethyl methacrylate.

Additional examples for lactamic monomers can be found in “A novel routeto substituted poly(vinyl pyrrolidone)s via simple functionalization of1-vinyl-2-pyrrolidone in the 3-position by ring-opening reactions” by H.Reinecke et. al. (Eur. Poly. 1, 46 (2010) p 1557-1562. Additionalexamples for lactamic monomers can be found in “Synthesis andpolymerization of new pyrrolidone-containing methacrylate monomers” byT. P. Davis et. al. (Polymer, 39, 17, p 4165-4169, 1998).

Accordingly, new polymeric inks are desirable having improved propertiesincluding solution viscosity, lubricity, gloss, cure speed, adhesion,impact resistance, toughness, coating hardness, water resistance,pigment surface decoration, tack, surface tension, wetting, foaming,tensile strength, solvency, dispersive properties, flexibility, chemicalresistance, abrasion resistance, and penetration.

SUMMARY OF THE INVENTION

The present invention provides polymers containing an acetoacetatemoiety having the following structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent.

The present invention further provides polymers containing anacetoacetate moiety having the following structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; y and z are mole percent,the sum of which=100%.

The polymers of the present invention may be employed in a wide varietyof compositions.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides polymers containing an acetoacetatemoiety. The polymers may be readily functionalized and thefunctionalized polymers may be further derivatized to provide a widevariety of useful polymers having desirable chemical and physicalproperties.

In one embodiment, the polymers comprise a monomer derived from maleicanhydride (cis-butenedioic anhydride), a monomer containing anacetoacetate moiety, and optionally a monomer to provide desirablecharacteristics in the polymer for use in a wide variety ofcompositions. The monomer derived from maleic anhydride provides a widerange of useful properties because of the ability to fully or partiallyhydrolyze maleic anhydride to produce carboxylic acids, esters, salts,half acids, half esters, half salts, and mixtures thereof. Dependingupon the type and amount of monomers selected and the degree and type ofhydrolyzed maleic anhydride, a wide variety of water-soluble andwater-insoluble polymers may be prepared. The monomer containing anacetoacetate moiety provides a monomer that can be functionalized with awide variety of groups to change the physical and chemical properties ofthe polymer. The acetyl group (CH₃CO—) present in the acetoacetatemoiety is thermally and photically labile. Upon heating or exposure tolight, this group can decompose, resulting in the formation of a radicalthat can form “macro-initiator” or “self-initiator” polymers. Themonomer that can provide desirable characteristics in the polymer may beselected from a wide variety of groups to provide desirablechemical/physical characteristics in the polymer. The monomer that canprovide desirable characteristics may comprise C₁-C₃₀ functionalized andunfunctionalized alkyls, alkenyls, alkoxyls, amides, aryls, carbonyls,carboxyls, cycloalkyl groups, moieties derived from trialkoxyvinylsilanes, and mixtures thereof; any of the before mentioned groups may bewith or without heteroatoms.

In another embodiment, the polymers comprise a monomer containing anacetoacetate moiety and a monomer to provide desirable characteristicsin the polymer for use in a wide variety of compositions.

The monomers containing an acetoacetate moiety may require no or verylittle photic or heat initiators, depending upon the particular polymer.The “macro-initiator” or “self-initiator” polymers may then be reactedvia a polymerization reaction with a variety of monomer moietiescomprising a functional group capable of “addition polymerization” as aresult of exposure to a free radical. Examples of suitable “additionpolymerizable” monomers include styrenics, vinylics, acrylates, maleics,maleimides, dienes, etc. Further moieties suitable for derivatizationinclude those disclosed in Eastman brochure Publication N-319C, December1999 entitled “Acetoacetoxyethyl Methacrylate (AAEM) AcetoacetylChemistry, which disclosure is incorporated by reference herein. Insightto addition polymerization processes and techniques can be found in“Principles of Polymer Chemistry” by Paul J. Flory (Cornell UniversityPress, Ithaca, N.Y., 1953), which disclosure is incorporated byreference herein. Further insight can also be found in “Principles ofPolymerization, 4^(th) Ed.” by George Odian (J. Wiley and Sons, Hoboken,N.J., 2004), which disclosure is incorporated by reference herein.Properties of many useful monomers can be found in the “PolymerHandbook, 4^(th) Ed.,” edited by J. Brandrup et. al. (J. Wiley and Sons,New York, 1999), which disclosure is incorporated by reference herein.

The monomers that can provide desirable characteristics in the polymersmay further include hydroxyethyl acrylate (HEA), hydroxyethylmethacrylate (HEMA), hydroxybutyl acrylate (HBA), ethyl hexylmethacrylate (EHMA), phenoxy ethyl acrylate (PEA), vinylene carbonate,hydroxyethyl pyrrolidone methacrylate, vinyl acetate (VA), ethylacrylate, methyl acrylate, iso(butyl) (meth)acrylates,methylmethacrylate, dimethylaminoethyl methacrylate (DMAEMA),dimethylaminopropyl methacrylamide (DMAPMA), 2-(2-ethoxyethoxy)ethylacrylate (EOEOEA), lauryl acrylate (LA), Stearyl acrylate (SA), acrylicacid-2-ethylhexyl ester, isodecyl acrylate, diacetone acrylamide,acryloyl morpholine (ACMO),3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),4-hydroxybutyl acrylate, (3-acrylamidopropyl)trimethylammonium chloride(APTAC), isodecyl acrylate (ISODA), lauryl methacrylate (LM), stearylmethacrylate (SM), 2,2,2-trifluoroethyl methacrylate,2-acrylamido-2-methyl-1-propanesulfonic acid,2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt,[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide,[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt, acrylamide, methacrylamide, acrylonitrile, isobornylacrylate, cyanoacrylates, C8-C10 acrylate (ODA), ethylene, styrene,C₈-C₁₀ acrylate, highly branched vinyl ester, maleic anhydride (MAN),acrylic acid (AA), sodium vinylsulfonate, diacetone acrylamide, vinylcarbonate, mono-acrylated glycols, vinyl ethylene carbonate, vinylchloride, 4-vinyl aniline, vinylpyridine, trimethylvinylsilane, vinylpropionate, crotonic acid, polyfunctional acrylates, polyfunctionalallyl ethers, vinyl imidazole, N-vinyl imidazole, glycidyl methacrylate(GMA) and allyl acetate and allyl alcohol.

In another aspect, the present invention provides polymers containing anacetoacetate moiety useful in a wide variety of compositions includingadhesives, aerosols, agricultural compositions, anti-soil redepositionagents, batteries, beverages, biocides, block copolymers, branchedcopolymers, cementing compositions, cleaning compositions, coatingcompositions, conductive materials, comb copolymers, cosmeticcompositions, cross-linkers, decorated pigment surfaces, dentalcompositions, detergents, dispersants, drugs, electronics,encapsulations, foods, graft copolymers, hair sprays,household-industrial-institutional (HI&I), inks and coatings (suitablefor use as a moisture resistant inkjet recording medium), interlaminateadhesives, lithographic solutions, membrane additive compositions, metalworking fluids, oilfield compositions, paints, paper, personal care andhygiene compositions, pharmaceuticals, pigment additives, plasters,plastics, printing, reactive biocides, refractive index modifiers,sequestrants, soil release compositions, static control agents,surfactants, and wood-care compositions.

Personal care compositions refers to such illustrative non-limitingcompositions as cosmetics, drug delivery systems, hair, oil,pharmaceuticals, pigment dispersions, preservative compositions,including those to alter the color and appearance of the skin, skin,sun, and tissue regeneration scaffolds. Other personal care compositionsinclude, but are not limited to, modified natural oils for increasedflexibility in styling, durable styling, increased humidity resistancefor hair, skin, and color cosmetics, sun care water-proof/resistance,wear-resistance, shower gels, shampoos, and thermal protecting/enhancingcompositions. Dental personal care compositions include dentureadhesives, toothpastes, mouth washes, and the like. Pharmaceuticalcompositions include tablet coatings, tablet binders, transdermalpatches, and the like. The wide variety of compositions are describedbelow in detail.

As used herein, the following terms have the meanings set out below.

The term “acetoacetate moiety” refers to the group

wherein R′ is defined herein. The CH₃—CO— moiety in the acetoacetatemoiety is thermally and photically labile.

The term “acidic conditions” refers to conditions relating to the pHvalue of an aqueous solution. Pure water is considered to be neutral,with a pH close to 7.0 at 25° C. Solutions with a pH value less than 7are considered to be acidic solutions.

The term “are each independently selected from the group consisting of”means that when a group appears more than once in a structure, thatgroup may be independently selected each time it appears. For example,in the structure below:

R₁-R₅ each appear more than once. The term “are each independentlyselected from the group consisting of” means that each R₁-R₅ group maybe the same or different.

The term “basic conditions” refers to conditions relating to the pHvalue. Pure water is considered to be neutral, with a pH close to 7.0 at25° C. Solutions with a pH value greater than 7 are considered to bebasic or alkaline.

The term “branched and unbranched alkyl groups” refers to alkyl groups,which may be straight chained or branched. For example, the alkyl groupshave from 1 to about 18 carbon atoms, more particularly, from 1 to about10 carbon atoms, and yet more particularly from 1 to about 6 carbonatoms. Branched groups include isopropyl, tert-butyl, and the like.

The term “condensation reaction” refers to a chemical reaction in whichtwo molecules or moieties (functional groups) combine to form one singlemolecule, together with the loss of a small molecule. When this smallmolecule is water, the reaction is known as a dehydration reaction.

The term “copolymer” refers to chains comprising more than one type ofmonomer unit.

The term “halogen” refers to chloro, bromo, iodo and fluoro, and in oneembodiment is bromo and/or chloro.

The term “heteroatom” refers to atoms such as oxygen, nitrogen, sulfur,and phosphorous. When the heteroatom is a nitrogen atom, the nitrogenatom may be present in the form of a quaternary amine.

The term “hydrolyzing” refers to a hydrolysis reaction (hydrolysis) inwhich a parent molecule is split into two parts by the addition of amolecule of water. During the hydrolysis reaction, molecules of waterare split into hydrogen cations (H⁺) and hydroxide anions (OH⁻). Onefragment of the parent molecule gains a hydrogen cation from the watermolecule; the other fragment gains the hydroxide anion.

The term “imide” refers to an organic compound comprising two carbonylgroups (acyl groups) bound to nitrogen atom. The nitrogen atom in theimide functional group may or may not be substituted with an organicfunctional group.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “intermediate compound” refers to a compound, which is producedduring the course of a chemical synthesis. An intermediate compound isnot itself, the final product, but is used in further reactions, whichproduce the final product. This is in contrast to the starting materialand final product. An intermediate compound is generally not isolated orpurified but rather is used “as is” in the synthesis. Many differentintermediate compounds may be produced during the course of a synthesis,especially for economical reasons on the industrial level.

The term “lactam” refers to a cyclic amide, which generally can containfrom 4-7 ring atoms in total.

The term “maleic anhydride” (cis-butenedioic anhydride, toxilicanhydride, 2,5-dioxofuran) is an organic compound with the formulaC₂H₂(CO)₂O. Maleic anhydride is the acid anhydride of maleic acid and inits pure state it is a colorless or white solid with an acrid odor.Maleic anhydride has the structure:

The term “maleimide” is the chemical compound with the formulaH₂C₂(CO)₂NH. Maleimide is an unsaturated imide, which is an importantbuilding block in organic synthesis. The name is a contraction of maleicacid and imide, the —C(O)NHC(O) functional group. Maleimide has thestructure:

The term “Michael addition” or “Michael reaction” generally refers tothe nucleophilic addition of a carbanion or another nucleophile to analpha, beta unsaturated carbonyl compound (electrophile).

The term “mineral acid” refers to an acid derived from one or moreinorganic compounds. Mineral acids release hydrogen ions when dissolvedin water. Commonly used mineral acids are sulfuric acid, hydrochloricacid, and nitric acid.

The term “monomer” refers to the repeat units comprising a polymer. Amonomer is a small molecule that chemically bonds to other monomers toform a polymer.

The term “non-homopolymer” refers to a polymer formed from two or moremonomers and includes essentially all polymers that are nothomopolymers. Nonlimiting examples of non-homopolymers includecopolymers, terpolymers, tetramers, and the like, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The term “oligomer” refers to a polymer molecule consisting of only afew monomeric units that are connected by covalent bond. For example,dimers, trimers, tetramers, etc. The term “polymer” refers to a largemolecule (macromolecule) composed of repeating structural units(monomers) connected by covalent chemical bonds. The terms oligomer andpolymer are used interchangeably herein.

The term “ODA” refers to octyl/decyl acrylate, which is a mixture ofn-octyl acrylate and n-decyl acrylate, the structures of which are setout below, respectively. The % composition of each component in themixture is about 30%-70%, by weight.

The term “pH” refers to a measure of the acidity or basicity of anaqueous solution. Pure water is considered to be neutral, with a pHclose to 7.0 at 25° C. Solutions with a pH less than 7 are considered tobe acidic and solutions with a pH greater than 7 are considered to bebasic or alkaline.

The term “pharmaceutically acceptable,” such as pharmaceuticallyacceptable carrier, excipient, etc., means pharmacologically acceptableand substantially non-toxic to the subject to which the particularcompound is administered.

The term “pharmaceutically acceptable salt” refers to conventionalacid-addition salts or base-addition salts that retain the biologicaleffectiveness and properties of the compounds of the present inventionand are formed from suitable non-toxic organic or inorganic acids ororganic or inorganic bases. Sample acid-addition salts include thosederived from inorganic acids such as hydrochloric acid, hydrobromicacid, hydroiodic acid, sulfuric acid, sulfamic acid, phosphoric acid andnitric acid, and those derived from organic acids such asp-toluenesulfonic acid, salicylic acid, methanesulfonic acid, oxalicacid, succinic acid, citric acid, malic acid, lactic acid, fumaric acid,and the like. Sample base-addition salts include those derived fromammonium, potassium, sodium, and quaternary ammonium hydroxides, such asfor example, tetramethylammonium hydroxide. Chemical modification of apharmaceutical compound (i.e., drug) into a salt is a technique wellknown to pharmaceutical chemists to obtain improved physical andchemical stability, hydroscopicity, and solubility of compounds. See,e.g., H. Ansel et. al., Pharmaceutical Dosage Forms and Drug DeliverySystems (6^(th) Ed. 1995) at pp. 196 and 1456-1457.

The term “polymerization” refers to methods for chemically reactingmonomer compounds to form polymer chains. The polymer chain may bealternating, blocked, or random. The type of polymerization method maybe selected from a wide variety of methods. Such methods include, butare not limited to, free radical polymerization methods, such asclassical radical polymerization and controlled radical polymerization,Nitroxide Mediation Polymerization (NMP), Atom Transfer RadicalPolymerization (ATRP), and Reversible Addition FragmentationChain-Transfer (RAFT).

The term “respectively” is a term that denotes that the items in a listcorrespond to each other in the order they are given. With reference totwo or more items, the term refers in a parallel or sequential manner.

The present invention provides polymers containing an acetoacetatemoiety having the following structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent.

Preferably, each R₁ and R₂ are independently hydrogen or methyl; R₃ is—C(O)OCH₂CH₂—; each R₄ is independently selected from the groupconsisting of functionalized and unfunctionalized alkoxy, amide, aryl,carbonyl, carboxyl, cycloalkyl groups, and moieties derived fromtriethoxyvinyl silane, wherein any of the before mentioned groups may bewith or without heteroatoms, and mixtures thereof; each R₅ isindependently selected from the group consisting of C₁-C₈ functionalizedand unfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; w ranges from 1-99%, y ranges from 1-99%, and z ranges from0-98%; more preferably w ranges from 1-60%, y ranges from 1-60%, and zranges from 0-80%; most preferably w ranges from 1-50%, y ranges from1-50%, and z ranges from 0-80%.

Preferably, the polymer has a structure selected from the groupconsisting of:

The present invention further provides polymers containing anacetoacetate moiety having the following structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; y and z are mole percent,the sum of which=100%.

Preferably, each R₁ and R₂ are independently hydrogen or methyl; R₃ is—C(O)OCH₂CH₂—; each R₄ is independently selected from the groupconsisting of functionalized and unfunctionalized alkoxy, amide, aryl,carbonyl, carboxyl, cycloalkyl groups, and moieties derived fromtriethoxyvinyl silane, wherein any of the before mentioned groups may bewith or without heteroatoms, and mixtures thereof; each R₅ isindependently selected from the group consisting of C₁-C₈ functionalizedand unfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; y ranges from 1-99% and z ranges from 1-99%; more preferably yranges from 1-80% and z ranges from 1-80%; most preferably y ranges from1-60% and z ranges from 1-60%.

Preferably, the polymer has a structure selected from the groupconsisting of:

The present invention discloses reactive co-solvents. These materialsconsist of (meth)acryl monomers or pre-polymers, a (meth)acryl ester ofan epoxy type monomer or pre-polymer, and a urethane type monomers orpre-polymers.

Examples of reactive co-solvents include but are not limited to2-hydroxy methyl methacrylate (HEMA), 2-hydroxy ethyl acrylate (HEA),2-phenoxy ethyl acrylate (PEA), 2-ethylhexyl-diglycol acrylate,2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), lauryl acrylate (LA), Stearylacrylate (SA), isobornyl acrylate (IBOA), acrylic acid-2-ethylhexylester, isodecyl acrylate, diacetone acrylamide, acryloyl morpholine(ACMO), cyclic trimethylol-propane formal acrylate (CTFA),3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),4-hydroxybutyl acrylate, (3-Acrylamidopropyl)trimethylammonium chloride(APTAC), C8-C10 acrylate (ODA), isodecyl acrylate (ISODA), laurylmethacrylate (LM), stearyl methacrylate (SM), 2,2,2-Trifluoroethylmethacrylate, 2-Acrylamido-2-methyl-1-propanesulfonic acid,2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt,[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide,[3-(Methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt, 1,6-hexanediol diacrylate (HDDA), dipropylene glycoldiacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), water,alcohol, hydro-alcohol mixtures, 1,4-butanediol diacrylate (BDDA),Tripropylene glycol diacrylate (TPGDA), dipropyleneglycol diacrylate(DPGDA), Tripropylene glycol diacrylate (TRPGDA), 1,9-nonanedioldiacrylate (NKDA), neopentyl glycol diacrylate (NPGDA), propoxylatedneopentyl glycol diacrylate (NPG2PODA), polyethylene glycol (200)diacrylate (PEG(200)DA), polyethylene glycol (400) diacrylate(PEG(400)DA), polyethylene glycol (600) diacrylate (PEG(600)DA),ethoxylated bisphenol-A diacrylate (BPA2EODA), triethylene glycoldiacrylate (TEGDA), triethylene glycol dimethacrylate (TEGDMA), glycerolpropoxylated triacrylate (GPTA), diethylene glycol dimethacrylate(DEGDMA), ethoxylated bisphenol-A dimethacrylate (BPA10EODMA),trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate(PET3A), ethoxylated tri-methylolpropane triacrylate (TMP3EOTA),propxylated tri-methylolpropane triacrylate (TMP3POTA), propoxylatedglyceryl triacrylate (GPTA), trimethylolpropane trimethylacrylate(TMPTMA), ethoxylated trimethylolpropane trimethacrylate (TMP3EOTMA),2,2-dionol diacrylate, pentaerythritol tetraacrylate (PETA),neopentylglycol diacrylate hydroxypivalate, 2-acryloyloxyethylphthalicacid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid,dimethyloltricyclodecane diacrylate, 2-acryloyloxyethylsuccinic acid,nonylphenol ethylene oxide adduct acrylate, phenol acrylates,methoxy-polyethylene glycol acrylate, tetramethylolmethane triacrylate,dipentaerythritol hexaacrylate (DPHA), isocyanate-functional unsaturatedacrylic ester resin, urethane diacrylates oligomers, urethane acrylates,modified urethane acrylates, polyester acrylates, modified bisphenol Adiacrylate, phenoxy-polyethylene glycol acrylate, bisphenol A propyleneoxide modified diacrylate, bisphenol A ethylene oxide adduct diacrylate,pentaerythritol triacrylate hexamethylenediisocyanate, urethaneprepolymer, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate,carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,glycidyl acrylates, acrylamides, polyfunctional acrylamides,polyfunctional (polyethylene glycol) acrylates, polyfunctional vinylamides, 1,4-butane-diol-monoacrylate and/or diglycidyl ether of1,4-butanediol, and the like. Mixtures of monomers are also envisionedin the present invention.

Additional examples include methyl vinylether, ethyl vinylether, propylvinylether, n-butyl vinylether, t-butyl vinylether, 2-ethylhexylvinylether, n-nonyl vinylether, lauryl vinylether, cyclohexylvinylether, cyclohexylmethyl vinylether, 4-methylcyclohexylmethylvinylether, benzyl vinylether, dicyclopentenyl vinylether,2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinylether,ethoxyethyl vinylether, butoxyethyl vinyl ether, methoxyethoxyvinylether, ethoxyethoxyethyl vinylether, methoxypolyethylene glycolvinylether, tetrahydrofurfuryl vinylether, dodecyl vinylether,diethylene glycol monovinylether, 2-hydroxyethyl vinylether,2-hydroxypropyl vinylether, 4-hydroxybutyl vinylether,4-hydroxymethylcyclohexylmethyl vinylether, polyethylene glycolvinylether, chloroethyl vinylether, chlorobutyl vinylether, phenylethylvinylether, phenoxypolyethylene glycol vinylether, ethylene glycoldivinylether, butylenes glycol divinylether, hexandiol divinylether,bisphenol A alkyleneoxide divinylethers, bisphenol F alkyleneoxidedivinylethers, propyleneoxide adducts of trimethylolpropanetrivinylether, triethylene glycol divinylether, cyclohexane dimethanoldivinylether, N-vinyl-2-pyrrolidone (VP), N-vinyl caprolactam (VCap),N-vinyl imidazole (VI), n-vinyl amides, 4-vinyl pyridine, 2-vinylpyridine, styrene, 5-vinyl-2-norbornene and the like.

The non-limiting examples of monofunctional epoxy compounds includephenyl glycidylether, p-tert-butylphenyl glycidylether, butylglycidylether, 2-ethylhexyl glycidylether, allyl glycidylether,1,2-butyleneoxide, 1,3-butadienemonooxide, 1,2-epoxydodecane,epichlorohydrin, 1,2-epoxydecane, styreneoxide, cyclohexeneoxide,3-methacryloyloxymethylcylcohexeneoxide,3-acryloyloxymethylcylcohexeneoxide, 3-vinylcylcohexeneoxide, and thelike.

The non-limiting examples of multifunctional epoxy compounds include3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,3-ethyl-3-((ethyloxetane-3-yl)methoxy) methyl)oxetane, bisphenol Adiglycidylether, bisphenol F diglycidylether, bisphenol Sdiglycidylether, brominated bisphenol A diglycidylether, brominatedbisphenol F diglycidylethers, brominated bisphenol S diglycidylether,epoxy novolak resins, hydrogenated bisphenol A diglycidylethers,hydrogenated bisphenol F diglycidylethers, hydrogenated bisphenol Sdiglycidylethers,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane,bis(3,4-epoxycyclohexylmethyl) adipate, vinylcylcohexeneoxide,4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, methylene-bis(3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctyl phthalate,epoxyhexahydrodi-2-ethylhexyl phthalate, 1,4-butanediol diglycidylether,1,6-hexanediol diglycidylether, glycerol triglycidylether,trimethylolpropane triglycidylether, polyethylene glycoldiglycidylether, polypropylene glycol diglycidylether,1,1,3-tetradecadienedioxide, limonenedioxide, 1,2,7,8-diepoxyoctane,1,2,5,6-diepoxycyclooctane, and the like.

The present invention relates to curing or cross-linking or polymerizinga polymerizable material is carried out by any appropriate method knownor explored in the prior-arts by a person skilled in the art. Insight tocuring and cross-linking technology is further disclosed in“Thermosetting Polymers,” J. P. Pascault et. al. (Marcel Dekker, NewYork, 2002) and is referred and disclosed herein in its entirety.Particularly, the polymerization of reactive solution comprisingpolymerizable polymer is carried out by employing any one of the methoddisclosed in “Principles of Polymerization 4^(th) edition,” by GeorgeOdian (J. Wiley and Sons, Hoboken, N.J., 2004) and is referred anddisclosed herein in its entirety. The preferable techniques or methodsemployed by the present invention to polymerize the polymers wouldinclude UV-radiation, UV-LED, laser beam, electron beam, gammairradiation, free-radical, cationic, anionic, thermal, exposure toe-beam and/or by employing a high-energy source in presence of suitablephoto initiator for the initiation of polymerization. Suitable source ofradiation including but not limited to mercury, xenon, halogen, carbonarc lamps, sunlight, and radioactive sources.

The present invention relates to material suitable for decorating(functionalizing or surface modification) the surface of a pigment. Apigment is defined as an insoluble substance, in solvent or water thatis a particule. Often it is desirable to decorate the pigment surface inorder to impart new and useful properties. For example, K. Holmberg et.al. describes technology related to surface modifications of aluminium(inorganic) pigments in Adv. Colloidal and Interface Sci. 128-130 (2006)121-134, and is referred and disclosed herein in its entirety.Additionally, organic pigments, such as polyvinyl polypyrrolidone(PVPP), are not easily functionalized. Incorporation of acetoacetatefunctionality provides for many decoration approaches to functionalizingthe surface of such particles, with either new organic and/or inorganicfeatures.

In order to induce polymerization via irradiation, often an appropriatephotoinitiator(s), which has high storage stability after being added,are incorporated to initiate the polymerization reaction system.Preferable photoinitiators are selected from the following non-limitinggroup or class of compounds such as2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenylketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morphorinopropane-1-on;benzoins e.g. benzyl dimethyl ketal; benzophenones such as benzophenone,4-phenylbenzophenone, and hydroxybenzophenone; thioxanthones such asisopropylthioxanthone and 2,4-diethylthioxanthone; acylphosphine oxides;and other special initiators such as methyl phenyl glyoxylate;bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide], a mixtureof bis[4-diphenylsulfonio]phenyl)sulfide bis(hexafluoroantimonate anddiphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate,bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)phenyl sulfide],5-2,4-cyclopentadiene-1-yl-[(1,2,3,4,5,6-.eta.)-(1-methylethyl-)benzene]-iron(1+)-hexafluorophosphate(1-)), 4-(2-hydroxytetradecanyloxy)diphenyliodonium hexafluoroantimonate, (4-hydroxynaphtyl)dimethylsulfonium hexafluoroantimonate), photo latent bases such asphoto latent diazabicyclo nonene, triphenylsulfoniumhexafluorophosphate, triphenylsulfonium hexafluoroantimonate,4-methoxyphenyldiphenylsulfonium hexafluoroantimonate,4-methoxyphenyliodonium hexafluoroantimonate,bis(4-tert-butylphenypiodonium tetrafluoroborate,(bis(4-tert-butylphenyl)iodonium hexafluorophosphate),(bis(4-tert-phenyl)iodonium hexafluoroantimonate),(bis[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate)),Aryldiazonium salts, diaryliodonium salts, triaylsulfonium salts,triarylselenonium salts, dialkylphenacylsulfonium salts,triarylsulfoxonium salts, triethanol amine, aryloxydiarylsulfoniumsalts, and the like for example, triphenylsulfonium hexaflurophosphate,methyidiphenylsulfonium hexafluorophosphate, dimethylphenylsulfoniumhexaflurophosphate, diphenyinapththylsulfonium hexaflurophosphate,di(methoxynapththyl)methylsulfonium hexaflurophosphate,(4-octyloxyphenyl) phenyl iodonium hexafluoro antimonate,(4-octyloxyphenyl) diphenyl sulfonium hexafluoro antimonate,(4-decyloxyphenyl) phenyl iodonium hexafluoro antimonite,(4-dodecyloxyphenyl)diphenyl sulfonium hexafluoroantimonate.Particularly, employed photoinitiators include10-biphenyl-4-yl-2-isopropyl-9H-thixanthen-10-ium hexaflurophosphate,4,4′-dimethyl iodonium hexaflurophosphate, mixed triarylsulfoniumhexaflurophosphate salts and reaction products of polyol and10-(2-carboxymethoxy)-biphenyl-4yl-2-isopropyl-9-oxo-9H-thioxanthen-10-iumhexaflurophosphate. Further, these photoinitiators are used alone or incombination thereof. Alternatively, if essential, the photoinitiator maybe used by mixing it with one or more photopolymerization accelerator,such as a benzoic acid (e.g., 4-dimethylaminobenzoic acid) or a tertiaryamine (e.g., diazabicyclo nonene (DBN)), in any appropriate ratio. Thephotoinitiator is preferably added to the photopolymerizable compositionin the range of about 0.1% to about 20% by weight.

In order to induce the Michael Addition, often an appropriate base isrequired. Preferable bases include diazabicyclo nonene (DBN),diazabicyclo undecene (DBU), tetramethylguanidine (TMG), sodiumhydroxide (NaOH), potassium hydroxide (KOH) and the like. Additionalinsight to suitable bases can be found in “Super Bases for OrganicSynthesis” edited by T. Ishikawa (J. Wiley and Sons, West Sussex, U K,2009.

According to one embodiment of the present invention, the polymerizablematerial reacted through free-radical polymerization in presence of afree-radical initiator. It refers to any chemical moiety, which, uponexposure to an appropriate energy source (e.g. light or heat) decomposesin to two independent uncharged fragments left with highly reactive oneunpaired electron. The contemplated free radical initiator forpolymerization would include but are not limited to various derivativesof peroxides, peresters and/or azo compounds. More particularly,selected from the group consisting of dicumyl peroxide, dibenzoylperoxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butylperoxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, bis(tert-butylperoxyisopropyl)benzene, and tert-butyl hydroperoxide), diacylperoxides, cumene hydroperoxide, dialkyl peroxides, hydroperoxides,ketone peroxides, monoperoxycarbonates, peroxydicarbonates,peroxyesters, and peroxyketals, including tertiary butyl perbenzoate,tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide indimethyl phthalate, dibenzoyl peroxide, 1-hydroxy cyclohexyl-1-phenylketone, bis (2,4,6-trimethyl benzoyl)phenyl phosphine, benzoin ethylether, 2,2-dimethoxy-2-phenyl acetophenone, di(p-chlorobenzoyl) peroxidein dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutylphthalate, dilauroyl peroxide, methyl ethyl ketone peroxide,cyclohexanone peroxide in dibutyl phthalate,3,5-dihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethylhexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, 1-hydroxy cyclohexyl hydroperoxide-1, t-butyl peroxy (2-ethylbutyrate), 2,5-dimethyl-2,5-bis(t-butyl peroxy) hexane, cumylhydroperoxide, diacetyl peroxide, t-butyl hydroperoxide, ditertiarybutyl peroxide, 3,5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, and1,1-bis(t-butyl peroxy)-3,3,5-trimethyl cyclohexane and di-(4-t-butylcyclohexyl) peroxydicarbonate, azo compounds such asazobisisobutyronitrile and azobiscyclohexanenitrile (e.g.,2,2′-azobis(2-methyl-propanenitrile),2,2′-azobis(2-methylbutanenitrile), and1,1′-azobis(cyclohexanecarbonitrile)) and the like mixtures andcombinations thereof. Alternatively, all of the above revealed freeradical initiator can be used for thermal based polymerization alone orappropriate mixture thereof and wherein, the polymerization reaction isinitiated through heat energy. Particular thermal initiator employed forthe polymerization of polymer would comprise 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′-azobis (2-methylpropanenitrile),2,2′-azobis (2-methylbutanenitrile), peroxides such as benzoyl peroxide,and the like. Preferably, the thermal initiator is2,2′-azobis(isobutyronitrile).

The structure of polymerizable polymer present in the reactive solutionis confirmed from appropriate spectral techniques that are known in theart and preferably employed spectral techniques would include ¹H-NMR,¹³C-NMR, and FT-IR spectra.

According to one embodiment of the present invention, a colorant may beadded. The colorant can be in the form of a pigments or dye.Combinations of pigments and dyes are also envisioned. Suitable pigmentmaterials are described in Hunger's “Industrial Organic Pigments,”Itoh's “Dictionary of Pigments,” and Leach and Pierce's “Printing InkManual.”

According to one embodiment of the present invention, a solvent may beadded. Suitable solvents are described in the “Industrial SolventsHandbook, 4^(th) Edition” edited by E. W. Flick (Noyes Data Corporation,Park Ridge, N.J., 1991), which disclosure is incorporated by referenceherein. For additional consideration of solvents, useful information isdescribed in “Polymer Handbook, 4^(th) Edition,” edited by J. Brandrupet. al. (J. Wiley and Sons, New York, 1999), which disclosure isincorporated by reference herein.

In one process for preparing a reactive solution comprising acetoacetatepolymer is (a) producing polymerizable polymer in a low boiling solvent,(b) eliminating the low boiling solvent at atmospheric or reducedpressure; and (c) replenishing with at least one higher boiling reactivesolvent. Wherein, the solvent is selected from polar and non-polarcategory. The typical non-limiting example of the solvents employed inthe process would include toluene, xylene, cyclohexanone, chlorobenzene,methyl ethyl ketone, dichloroethane, chloroform, chloromethane,dichloromethane, carbon tetrachloride, ethylene chloride,trichloroethane, ethyl acetate, n-propyl acetate, iso-propyl acetate,2-nitropropane, any form of water (distilled, deionized or tap) andwater miscible solvents such as tetrahydrofuran, acetone, dioxane,dimethyl formamide, dimethyl sulfoxide, ethanol, methanol, propanol,isopropanol, butanol, isobutanol, ethylene glycol, ethylene glycolmonomethyl ether, and propylene glycol. The solvent is eliminated fromthe reaction mixture employing suitable techniques that are known in theart to concentrate the reaction mixture, however, the preferable methodof elimination is boiling, distilling, evaporating with or withoutvacuum.

In another aspect, application of a wide variety of compositionscomprising the novel modified polymers are provided, includingadhesives, aerosols, agricultural compositions, anti-soil redepositionagents, batteries, beverages, biocides, block copolymers, branchcopolymers, cementing compositions, cleaning compositions, combcopolymers, coating compositions, conductive materials, cosmeticcompositions, cross-linkers, decorated pigment surfaces, dentalcompositions, detergents, dispersants, drugs, electronics,encapsulations, foods, graft copolymers, hair sprays,household-industrial-institutional (HI&I), inks and coatings (suitablefor use as a moisture resistant inkjet recording medium), interlaminateadhesives, lithographic solutions, membrane additive compositions, metalworking fluids, oilfield compositions, paints, paper, personal carecompositions, pharmaceuticals, pigment additives, plasters, plastics,printing, reactive biocides, refractive index modifiers, sequestrants,soil release compositions, static control agents, and wood-carecompositions.

Compositions belonging to the personal care/cosmetic and pharmaceuticalarts find utility in altering, delivering an active, enhancing,improving, modifying the appearance, condition, color, health, style ofthe skin (including face, scalp, and lips), hair, nails, and oralcavity. Many examples and product forms of these compositions are known.These compositions can impart benefits that include, but are not limitedto, hair style flexibility, hair style durability, humidity resistancefor hair, color and/or color protection, moisturization, wrinklereduction, protection from ultraviolet radiation, water proofness, waterresistance, wear resistance, thermal protection, adhesion, activeingredient delivery, anti-cavity, and/or anti-gingivitis protection. Assuch, these compositions are sometimes categorized in the followingareas: skin care, hair care (both styling and non-styling), sun care,cosmetics (including color cosmetics), antiperspirants, deodorants, oralhygiene, and men's and women's personal hygiene/grooming. In some casesthese benefits and care areas overlap with another.

Skin care compositions include those materials used on the body, face,hands, lips, and/or scalp, and are beneficial for many reasons, such asfirming, anti-cellulite, moisturizing, nourishing, cleaning, reducing oreliminating the appearance of wrinkles or lentigo, toning, and/orpurifying. They also can be used to sanitize.

Consumers can identify many of the compositions that serve the sun carearea, for example after-fun, children's, beach, self-tan, sports (i.e.,being sweatproof, waterproof, resistant to running, or having added UVabsorbers and/or antioxidants), sensitive skin products (i.e., havinglow irritation to the eyes and/or skin, and/or being free of fragrancesand/or dyes), daily wear, leave-on hair creams, lotions, stylingproducts, and hair sprays. Typically, sun care products also compriseone or more UV actives, which are those organic and inorganic materialsthat scatter, absorb, and/or reflect radiation having a wavelength fromabout 100 nm to about 400 nm. In one aspect, the sun care productprotects against UV-A and/or UV-B radiation. UV-A radiation, from about320 nm to about 400 nm, has the longest wavelength within the UVspectrum, and consequently is the least energetic. While UV-A rays caninduce skin tanning, they are liable to induce adverse changes as well,especially in the case of sensitive skin or of skin, which iscontinually exposed to solar radiation. In particular UV-A rays cause aloss of skin elasticity and the appearance of wrinkles, leading topremature skin aging. UV-B rays have shorter wavelengths, from about 290nm to about 320 nm, and their higher energy can cause erythema and skinburns, which may be harmful. Alternatively, sun care products may omitUV actives, and may be regarded as a tanning oil or a tan promoter. Somesun care compositions may promote soothe skin after sun exposure, and/orbe formulated for application to the lips, hair, or the area around theeyes. Self-tan compositions, which are products that color skin withoutrequiring full sun exposure, also fit under the sun care umbrella. Themany different sun care product formats include may assume a consistencyranging from liquid to semiliquid forms (e.g., milks, creams), tothicker forms like gels, creams, pastes, and even solid- and wax-likeforms. Sun care products also may take the form of an aerosol, spray,mist, roll-on, or wipe.

Hair care compositions include shampoos, leave-on and rinse-outconditioners used for conditioning, moisturizing, repairing, haircolors, hair relaxers, and deep conditioners and treatments such as hotoils and waxes, 2-in-1 shampoo/conditioner combination products, 3-in-1shampoo/conditioner/styling agent. The many types of hair care productscan be delivered in an array of formats, including aerosol sprays, pumpsprays, gel sprays, mousses, gels, waxes, creams, pomades, spritzes,putties, lacquers, de-frizzing serums, perms, relaxants and colorants.

Color cosmetic compositions include facial make-up, eye makeup,mascaras, lip and nail products. Facial make-up compositions includefoundation (liquid, solid, and semi-solid)—skin tinted creams, liquid,sticks, mousses used as a base under make-up, rouge, face powder,blusher, highlighters, face bronzers, concealers, and 2-way cakeproducts.

Personal care/cosmetics also include eye make-up, mascaras, eyeliners,eye shadows, eyebrow pencils and eye pencils. Lip products includelipsticks, lip pencils, lip gloss, transparent bases and tinted lipmoisturizers as well as multi-function color sticks that can also beused for cheeks and eyes. Nail products include nail varnishes/enamels,nail varnish removers, treatments, home-manicure products such ascuticle softeners and nail strengtheners.

In addition to the skin, hair, and sun care compositions summarizedabove, the polymers related herein also find application in oral carecompositions. Non-limiting examples or oral care compositions includetoothpastes (including toothpaste gels), denture adhesives, whiteners,anesthetics, and dental floss and related products. These compositionsmay take any product format, such as pastes, gels, creams, solutions,dispersions, rinses, flosses, aerosols, powders, and lozenges.

Grooming products for men and women include shaving products andtoiletries, which may find use in preparing the skin and/or hair for dryor wet shaving. In addition, these compositions may help to moisturize,cool, and/or soothe skin. A variety of product forms are known, a few ofwhich are foams, gels, creams, sticks, oils, solutions, tonics, balms,aerosols, mists, sprays, and wipes.

The polymer can also be used in other personal care/cosmeticapplications, such as an absorbent material in appropriate applicationssuch as diapers, incontinence products, feminine products, and otherrelated products.

The polymers described herein also find application in bath and showercompositions, such as foams, gels, salts, oils, balls, liquids, powdersand pearls. Also included are bar soaps, body washes, shower gels,cleansers, gels, oils, foams, scrubs and creams. As a natural extensionof this category, these compositions also include liquid soaps and handsanitizers used for cleaning hands.

The polymer of the invention can be used in combination with one or moreadditional personal care/cosmetically acceptable additives chosen from,for example, conditioning agents, protecting agents, such as, forexample, hydrosoluble, liposoluble and water-insoluble UV filters,antiradical agents, antioxidants, vitamins and pro-vitamins, fixingagents, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic and amphoteric surfactants, thickeners,perfumes, pearlizing agents, stabilizers, pH adjusters, filters,preservatives, hydroxy acids, various cationic, anionic and nonionicpolymers, cationic and nonionic polyether associative polyurethanes,vegetable oils, mineral oils, synthetic oils, polyols such as glycolsand glycerol, silicones, aliphatic alcohols, colorants, bleachingagents, highlighting agents and sequestrants.

For some embodiments, it may be preferred to add one or morepreservatives and/or antimicrobial agents, such as, but not limited to,benzoic acid, sorbic acid, dehydroacetic acid, piroctone olamine, DMDMhydantoin, IPBC, triclosan, bronopol, formaldehyde, isothiazolinones,nitrates/nitrites, parabens, phenoxyethanol, potassium sorbate, sodiumbenzoate, sulphites, and sulphur dioxide. Combinations of preservativesmay be used.

In other embodiments it may be desirable to incorporate preservativeboosters/solvents, select examples of which include caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, and glyceryl caprylate. Humectants, which include glycerin,butylene glycol, propylene glycol, sorbitol, mannitol, and xylitol maybe added. Polysaccharides, such as gum Arabic, may be included as well.It may be desirable to include one or more other ingredients, such asthose described in U.S. patent publication 2010/0183532 and WO2010/105050, which disclosures are incorporated herein by reference.

These additives may be present in the composition according to theinvention in proportions that may range from about 0% to about 20% byweight in relation to the total weight of the composition. The preciseamount of each additive may be easily determined by an expert in thefield according to its nature and its function.

Examples of these co-ingredients and many others can be found in thefollowing references, each of which is herein incorporated in itsentirety by reference: “Inventory and common nomenclature of ingredientsemployed in cosmetic products,” Official Journal of the European Union,5.4.2006, pages L 97/1 through L 97/528; and International CosmeticIngredient Dictionary and Handbook, 13^(th) edition, ISBN: 1882621476,published by The Personal Care Products Council in January 2010.

Any known conditioning agent is useful in the personal care/cosmeticcompositions of this invention. Conditioning agents function to improvethe cosmetic properties of the hair, particularly softness, thickening,untangling, feel, and static electricity and may be in liquid,semi-solid, or solid form such as oils, waxes, or gums. Similarly, anyknown skin-altering agent is useful in the compositions of thisinvention. A few examples of conditioning agents include cationicpolymers, cationic surfactants and cationic silicones. Conditioningagents may be chosen from synthesis oils, mineral oils, vegetable oils,fluorinated or perfluorinated oils, natural or synthetic waxes,silicones, cationic polymers, proteins and hydrolyzed proteins, ceramidetype compounds, cationic surfactants, fatty amines, fatty acids andtheir derivatives, as well as mixtures of these different compounds.

The synthesis oils include polyolefins, e.g., poly-α-olefins such aspolybutenes, polyisobutenes and polydecenes. The polyolefins can behydrogenated. The mineral oils suitable for use in the compositions ofthe invention include hexadecane and oil of paraffin. Suitable animaland vegetable oils include sunflower, corn, soy, avocado, jojoba,squash, raisin seed, sesame seed, walnut oils, fish oils, glyceroltricaprocaprylate, Purcellin oil or liquid jojoba. Suitable natural orsynthetic oils include eucalyptus, lavender, vetiver, litsea cubeba,lemon, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon,hyssop, caraway, orange, geranium, cade, and bergamot. Suitable naturaland synthetic waxes include carnauba wax, candelila wax, alfa wax,paraffin wax, ozokerite wax, vegetable waxes such as olive wax, ricewax, hydrogenated jojoba wax, absolute flower waxes such as blackcurrant flower wax, animal waxes such as bees wax, modified bees wax(cerabellina), marine waxes and polyolefin waxes such as polyethylenewax.

The cationic polymers that may be used as a conditioning agent accordingto the invention are those known to improve the cosmetic properties ofhair treated by detergent compositions. The expression “cationicpolymer” as used herein, indicates any polymer containing cationicgroups and/or ionizable groups in cationic groups. The cationic polymersused generally have a molecular weight the average number of which fallsbetween about 500 and 5,000,000, for example between 1000 and 3,000,000.Cationic polymers may be chosen from among those containing unitsincluding primary, secondary, tertiary, and/or quaternary amine groupsthat may either form part of the main polymer chain or a side chain.Useful cationic polymers include known polyamine, polyaminoamide, andquaternary polyammonium types of polymers, such as:

homopolymers and copolymers derived from acrylic or methacrylic estersor amides. The copolymers can contain one or more units derived fromacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides, acrylic or methacrylic acids or their esters,vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinylesters. Specific examples include: copolymers of acrylamide and dimethylamino ethyl methacrylate quaternized with dimethyl sulfate or with analkyl halide; copolymers of acrylamide and methacryloyl oxyethyltrimethyl ammonium chloride; the copolymer of acrylamide andmethacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers ofvinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionallyquaternized, such as the products sold under the name Gafquat® byInternational Specialty Products; the dimethyl amino ethylmethacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such asthe product sold under the name Gaffix® VC 713 by InternationalSpecialty Products; the vinyl pyrrolidone/methacrylamidopropyldimethylamine copolymer, marketed under the name Styleze® CC-10 byInternational Specialty Products; the vinyl pyrrolidone/quaternizeddimethyl amino propyl methacrylamide copolymers such as the product soldunder the name Gafquat® HS-100 by International Specialty Products; andthe vinyl pyrrolidone/dimethylaminopropyl methacrylamide/C₉-C₂₄alkyldimethylaminopropyl methacrylic acid quaternized terpolymersdescribed in U.S. Pat. No. 6,207,778 and marketed under the nameStyleze® W-20 by International Specialty Products.

derivatives of cellulose ethers containing quaternary ammonium groups,such as hydroxy ethyl cellulose quaternary ammonium that has reactedwith an epoxide substituted by a trimethyl ammonium group.

derivatives of cationic cellulose such as cellulose copolymers orderivatives of cellulose grafted with a hydrosoluble quaternary ammoniummonomer, as described in U.S. Pat. No. 4,131,576, such as the hydroxyalkyl cellulose, and the hydroxymethyl-, hydroxyethyl- orhydroxypropyl-cellulose grafted with a salt of methacryloyl ethyltrimethyl ammonium, methacrylamidopropyl trimethyl ammonium, or dimethyldiallyl ammonium.

cationic polysaccharides such as described in U.S. Pat. Nos. 3,589,578and 4,031,307, guar gums containing cationic trialkyl ammonium groupsand guar gums modified by a salt, e.g., chloride of 2,3-epoxy propyltrimethyl ammonium.

polymers composed of piperazinyl units and alkylene or hydroxy alkylenedivalent radicals with straight or branched chains, possibly interruptedby atoms of oxygen, sulfur, nitrogen, or by aromatic or heterocycliccycles, as well as the products of the oxidation and/or quaternizationof such polymers.

water-soluble polyamino amides prepared by polycondensation of an acidcompound with a polyamine. These polyamino amides may be reticulated.

derivatives of polyamino amides resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationby bi-functional agents.

polymers obtained by reaction of a polyalkylene polyamine containing twoprimary amine groups and at least one secondary amine group with adioxycarboxylic acid chosen from among diglycolic acid and saturateddicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Suchpolymers are described in U.S. Pat. Nos. 3,227,615 and 2,961,347.

the cyclopolymers of alkyl dialyl amine or dialkyl diallyl ammonium suchas the homopolymer of dimethyl diallyl ammonium chloride and copolymersof diallyl dimethyl ammonium chloride and acrylamide.

quaternary diammonium polymers such as hexadimethrine chloride. Polymersof this type are described particularly in U.S. Pat. Nos. 2,273,780,2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378,3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617,4,025,627, 4,025,653, 4,026,945, and 4,027,020.

quaternary polyammonium polymers, including, for example, Mirapol® A 15,Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 products sold by Miranol.

the quaternary polymers of vinyl pyrrolidone and vinyl imidazole such asthe products sold under the names Luviquat® FC 905, FC 550, and FC 370by BASF.

quaternary polyamines.

reticulated polymers known in the art.

Other cationic polymers that may be used within the context of theinvention are cationic proteins or hydrolyzed cationic proteins,polyalkyleneimines such as polyethyleneimines, polymers containing vinylpyridine or vinyl pyridinium units, condensates of polyamines andepichlorhydrins, quaternary polyurethanes, and derivatives of chitin. Inone aspect, the cationic polymers may be derivatives of quaternarycellulose ethers, the homopolymers and copolymers of dimethyl diallylammonium chloride, quaternary polymers of vinyl pyrrolidone and vinylimidazole, and mixtures thereof.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones suitable for useaccording to the invention include polyorganosiloxanes that areinsoluble in the composition. The silicones may be present in the formof oils, waxes, polymers, or gums. They may be volatile or non-volatile.The silicones can be selected from polyalkyl siloxanes, polyarylsiloxanes, polyalkyl aryl siloxanes, silicone gums and polymers, andpolyorgano siloxanes modified by organofunctional groups, and mixturesthereof. Suitable polyalkyl siloxanes include polydimethyl siloxaneswith terminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C₁-C₂₀) siloxanes. Suitable polyalkyl arylsiloxanes include polydimethyl methyl phenyl siloxanes and polydimethyldiphenyl siloxanes, linear or branched. The silicone gums suitable foruse herein include polydiorganosiloxanes including those having anumber-average molecular weight between 200,000 and 1,000,000, usedalone or mixed with a solvent. Examples include polymethyl siloxane,polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxaneand polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane.Suitable silicone polymers include silicones with a dimethyl/trimethylsiloxane structure and polymers of the trimethyl siloxysilicate type.The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical andgrafted siliconated polymers. In one embodiment the silicones are aminofunctional silicones. The silicones may be used in the form ofemulsions, nano-emulsions, or micro-emulsions.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havinggroups of quaternary ammonium on the polypeptide chain, including atleast one C₁-C₁₈ alkyl. Hydrolyzed proteins include Croquat™ L, in whichthe quaternary ammonium groups include a C₁₂ alkyl group, Croquat™ M, inwhich the quaternary ammonium groups include C₁₀-C₁₈ alkyl groups,Croquat™ S in which the quaternary ammonium groups include a C₁₈ alkylgroup and Crotein Q in which the quaternary ammonium groups include atleast one C₁-C₁₈ alkyl group. These products are sold by Croda. Theconditioning agent can comprise quaternized vegetable proteins such aswheat, corn, or soy proteins such as cocodimonium hydrolyzed wheatprotein, laurdimonium hydrolyzed wheat protein and steardimoniumhydrolyzed wheat protein.

The conditioning agent can be a ceramide type of compound such as aceramide, a glycoceramide, a pseudoceramide, or a neoceramide. Thesecompounds can be natural or synthetic. Compounds of the ceramide typeare, for example, described in patents pending DE4424530, DE4424533,DE4402929, DE4420736, WO95/23807, WO94/07844, EP-A-0646572, WO95/16665,FR-2 673 179, EP-A-0227994, WO 94/07844, WO 94/24097, and WO 94/10131.Ceramide type compounds useful herein include 2-N-linoleoylamino-octadecane-1,3-diol, 2-N-oleoyl amino-octadecane-1,3-diol,2-N-palmitoyl amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3-diol, 2-N-behenoyl amino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl N-cetyl) malonamide,N(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylic acid,N-docosanoyl N-methyl-D-glucamine and mixtures of such compounds.

The conditioning agent can be a cationic surfactant such as a salt of aprimary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimidazoline, or an amine oxide. Suitable examples include mono-, di-, ortri-alkyl quaternary ammonium compounds with a counter-ion such as achloride, methosulfate, tosylate, etc. including, but not limited to,cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and the like. The presence of a quaternary ammoniumcompound in conjunction with the polymer described above reduces staticand enhances combing of hair in the dry state. The polymer also enhancesthe deposition of the quaternary ammonium compound onto the hairsubstrate thus enhancing the conditioning effect of hair.

The conditioning agent can be any fatty amine known to be useful as aconditioning agent; e.g. dodecyl, cetyl or stearyl amines, such asstearamidopropyl dimethylamine. The conditioning agent can be a fattyacid or derivatives thereof known to be useful as conditioning agents.Suitable fatty acids include myristic acid, palmitic acid, stearic acid,behenic acid, oleic acid, linoleic acid, and isostearic acid. Thederivatives of fatty acids include carboxylic ester acids includingmono-, di-, tri- and tetra-carboxylic acids.

The conditioning agent can be a fluorinated or perfluorinated oil.Fluorinated oils include perfluoropolyethers described in EP-A-486135and the fluorohydrocarbon compounds described in WO 93/11103. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers. Ofcourse, mixtures of two or more conditioning agents can be used.

The conditioning agent or agents can be present in an amount from about0.001% to about 20%, particularly from about 0.01% to about 10%, andeven more particularly from about 0.1% to about 3% by weight based onthe total weight of the final composition. The personal care/cosmeticcompositions of the invention can contain one or more protecting agentsin combination with the above-described polymer to prevent or limit thedegrading effects of natural physical and/or chemical assaults on thekeratinous materials.

The protecting agent can be chosen from hydrosoluble, liposoluble andwater-insoluble UV filters, antiradical agents, antioxidants, vitaminsand pro-vitamins. The above-described cationic polymer enhances thedeposition of these materials onto the hair or skin substrate enhancingprotection of hair to UV damage. Organic UV filters (systems that filterout UV rays) can be chosen from among hydrosoluble or liposolublefilters, whether siliconated or nonsiliconated, and mineral oxideparticles, the surface of which may be treated. Hydrosoluble organic UVfilters may be chosen from para-amino benzoic acid and its salts,anthranilic acid and its salts, salicylic acid and its salts, hydroxycinnamic acid and its salts, sulfonic derivatives of benzothiazoles,benzimidizoles, benzoxazoles and their salts, sulfonic derivatives ofbenzophenone and their salts, sulfonic derivatives of benzylidenecamphor and their salts, derivatives of benzylidene camphor substitutedby a quaternary amine and their salts, derivatives ofphthalydene-camphosulfonic acids and their salts, sulfonic derivativesof benzotriazole, and mixtures thereof. Hydrophilic polymers, which havelight-protective qualities against UV rays, can be used. These includepolymers containing benzylidene camphor and/or benzotriazole groups.

Suitable liposoluble organic UV filters include derivatives ofpara-aminobenzoic acid, such as the esters or amides ofpara-aminobenzoic acid; derivatives of salicylic acid; derivatives ofbenzophenone; derivatives of dibenzoyl methane; derivatives of diphenylacrylates; derivatives of benzofurans; UV filter polymers containing oneor more silico-organic residues; esters of cinnamic acid; derivatives ofcamphor; derivatives of trianilino-s-triazine; the ethylic esterurocanic acid; benzotriazoles; derivatives of hydroxy phenyl triazine;bis-resorcinol-dialkyl amino triazine; and mixtures thereof. Theliposoluble (or lipophilic) organic UV filter can be chosen from octylsalicylate; 4-tert-butyl-4′-methoxy dibenzoyl methane; octocrylene;4-methoxy cinnamate; 2-ethylhexyl [2-ethylhexyl 4-methoxycinnamate]; and2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy] disiloxanyl]propynyl] phenol. Other UV filters that may beuseful are derivatives of benzophenones such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxy benzophenone,derivatives of benzalmalonates such as poly dimethyl/methyl(3(4-(2,2-bis-ethoxy carbonyl vinyl)-phenoxy)-propenyl) siloxane,derivatives of benzylidene camphor such as b-b′camphosulfonic [1-4divinylbenzene] acid and derivatives of benzimidazole such as2-phenyl-benzimidazol-5-sulfonic acid. Water-insoluble UV filtersinclude various mineral oxides. The mineral oxides may be selected fromamong titanium oxides, zinc oxides, and cerium oxides. The mineraloxides can be used in the form of ultrafine nanoparticles. For example,the UV filters can include Escalol® HP-610 (dimethylpabamido propyllaurdimonium tosylate and propylene glycol stearate) or Crodasorb HP(polyquaternium 59).

The antioxidants or antiradical agents can be selected from phenols suchas BHA (tert-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-p-cresol),TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodicoligomers, flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine, glutathione,superoxide dismutase, and lactoferrin.

The vitamins can be selected from ascorbic acid (vitamin C), vitamin E,vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5,vitamin PP, vitamin A, and derivatives thereof. The provitamins can beselected from panthenol and retinol.

The protecting agent can be present in an amount from about 0.001% toabout 20% by weight, particularly from about 0.01% to about 10% byweight, and more particularly from 0.1% to about 5% by weight of thetotal weight of the final composition.

The composition of the invention can contain a fixing agent incombination with the above-described polymer. The fixing agent can be ananionic polymer chosen from polymers containing carboxylic units derivedfrom unsaturated carboxylic mono- or polyacids of the formula:

in which n is a whole number from 0 to 10, A₁ denotes a methylene group,optionally bonded to the carbon atom of the unsaturated group or to aneighboring methylene group when n is greater than 1 by means of aheteroatom like oxygen or sulfur, R₇ denotes a hydrogen atom, a phenylor benzyl group, R₈ denotes a hydrogen atom, a lower alkyl or carboxylgroup, R₉ denotes a hydrogen atom, a lower alkyl group, a —CH₂—COOH,phenyl or benzyl group and polymers containing units derived fromsulfonic acid like vinylsulfonic, styrenesulfonic,acrylamidoalkylsulfonic units.

The fixing agent can be an amphoteric polymer chosen from the polymercontaining recurring units derived from:

at least one monomer chosen from acrylamides or methacrylamidessubstituted on the nitrogen with an alkyl radical,

at least one acid copolymer containing one or more reactive carboxylgroups, and

at least one basic comonomer, such as esters with primary, secondary,tertiary, and quaternary amino substituents of acrylic and methacrylicacids and the product of quaternization of dimethylaminoethylmethacrylate with dimethyl or diethyl sulfate.

The fixing agent can be a nonionic polymer chosen frompolyalkyloxazolines; vinyl acetate homopolymers; vinyl acetate andacrylic ester copolymers; vinyl acetate and ethylene copolymers; vinylacetate and maleic ester copolymers; polyethylene and maleic anhydridecopolymers; homopolymers of alkyl acrylates; homopolymers of alkylmethacrylates; copolymers of acrylic esters; copolymers of alkylacrylates and alkyl methacrylates; copolymers of acrylonitrile and anonionic monomer chosen from among butadiene and alkyl (meth)acrylates;copolymers of alkyl acrylate and urethane; and polyamides. The fixingagent can be a functionalized or unfunctionalized, silicone ornon-silicone polyurethane. The fixing polymer can be a polymer of thegrafted silicone type containing a polysiloxane portion and a portionconsisting of a nonsilicone organic chain, with one of the two portionsforming the main chain of the polymer, and with the other being graftedonto the main chain.

The fixing agent can be present in the composition in a relative weightconcentration between about 0.1% to about 10%, for example, from about0.5% to about 5%.

The personal care/cosmetic composition of the invention can contain anoxidizing agent in combination with the above-described polymer. Theoxidizing agent can be chosen from the group of hydrogen peroxide, ureaperoxide, alkali metal bromates, ferricyanides, persalts, and redoxenzymes, optionally with their respective donor or cofactor. Forexample, the oxidizing agent can be hydrogen peroxide. The oxidizingagent can be a solution of oxygenated water whose titer varies from 1 to40 volumes.

The personal care/cosmetic composition of the invention can contain atleast one reducing agent in combination with the above-described polymerin amounts from about 0.01% to about 30%, particularly from about 0.05%to about 20% of the total weight of the composition. The reducing agentscan be selected from thiols, like cysteine, thioglycolic acid,thiolactic acid, their salts and esters, cysteamine, and its salts orsulfites. In the case of compositions intended for bleaching, ascorbicacid, its salts and its esters, erythorbic acid, its salts and itsesters, and sulfinates, like sodium hydroxymethanesulfinate can be used.

The personal care/cosmetic composition of the invention can contain adye in combination with the above-described polymer. The dye can beselected from the group consisting of neutral acid or cationicnitrobenzene dyes, neutral acid or cationic azo dyes, quinone dyes,neutral, acid or cationic anthraquinone dyes, azine dyes, triarylmethanedyes, indoamine dyes and natural dyes. The dye or dyes can be present ina concentration from about 0.001% to about 20%, and particularly fromabout 0.005% to about 10% based on the total weight of the composition.

The personal care/cosmetic composition of the invention can contain atleast one amphoteric polymer or a cationic polymer in combination withthe above-described polymer. Suitable cationic polymers include apoly(quaternary ammonium) consisting of recurrent units corresponding tothe following formulae (W) and (U):

Suitable amphoteric polymers include a copolymer containing at least oneacrylic acid and a dimethyldiallyammonium salt as a monomer. Thecationic or amphoteric polymer or polymers can be present in an amountfrom about 0.01% to about 10%, particularly from about 0.05% to about5%, and more particularly from about 0.1% to about 3% by weight of thetotal weight of the composition.

In addition, the personal care/cosmetic compositions can include atleast one surfactant in combination with the above-described polymer.The surfactant can be present in an amount from about 0.1% to about 60%,particularly from about 1% to about 40%, and more particularly fromabout 5% to about 30% by weight based on the total weight of thecomposition. The surfactant may be chosen from among anionic,amphoteric, or non-ionic surfactants, or mixtures of them known to beuseful in personal care/cosmetic compositions.

One or more suitable thickeners or viscosity increasing agents may beincluded in combination with the above-described polymer in the personalcare/cosmetic compositions of the invention. Suitable thickeners and/orviscosity increasing agents include: Acetamide MEA;Acrylamide/Ethalkonium Chloride Acrylate Copolymer;Acrylamide/Ethyltrimonium Chloride Acrylate/Ethalkonium ChlorideAcrylate Copolymer; Acrylamides Copolymer; Acrylamide/Sodium AcrylateCopolymer; Acrylamide/Sodium Acryloyldimethyltaurate Copolymer;Acrylates/Acetoacetoxyethyl Methacrylate Copolymer;Acrylates/Beheneth-25 Methacrylate Copolymer; Acrylates/C10-30 AlkylAcrylate Crosspolymer; Acrylates/Ceteth-20 Itaconate Copolymer;Acrylates/Ceteth-20 Methacrylate Copolymer; Acrylates/Laureth-25Methacrylate Copolymer; Acrylates/Palmeth-25 Acrylate Copolymer;Acrylates/Palmeth-25 Itaconate Copolymer; Acrylates/Steareth-50 AcrylateCopolymer; Acrylates/Steareth-20 Itaconate Copolymer;Acrylates/Steareth-20 Methacrylate Copolymer; Acrylates/StearylMethacrylate Copolymer; AcrylatesNinyl Isodecanoate Crosspolymer;Acrylic Acid/Acrylonitrogens Copolymer; Adipic Acid/Methyl DEACrosspolymer; Agar; Agarose; Alcaligenes Polysaccharides; Algin; AlginicAcid; Almondamide DEA; Almondamidopropyl Betaine; Aluminum/MagnesiumHydroxide Stearate; Ammonium Acrylates/Acrylonitrogens Copolymer;Ammonium Acrylates Copolymer; Ammonium Acryloyldimethyltaurate/VinylFormamide Copolymer; Ammonium AcryloyldimethyltaurateNP Copolymer;Ammonium Alginate, Ammonium Chloride; Ammonium PolyacryloyldimethylTaurate; Ammonium Sulfate; Amylopectin; Apricotamide DEA;Apricotamidopropyl Betaine; Arachidyl Alcohol; Arachidyl Glycol; ArachisHypogaea (Peanut) Flour; Ascorbyl Methylsilanol Pectinate; AstragalusGummifer Gum; Attapulgite; Avena Sativa (Oat) Kernel Flour; AvocadamideDEA; Avocadamidopropyl Betaine, Azelamide MEA; Babassuamide DEA;Babassuamide MEA; Babassuamidopropyl Betaine; Behenamide DEA; BehenamideMEA, Behenamidopropyl Betaine; Behenyl Betaine; Bentonite; ButoxyChitosan, Caesalpinia Spinosa Gum; Calcium Alginate; CalciumCarboxymethyl Cellulose; Calcium Carrageenan; Calcium Chloride; CalciumPotassium Carbomer; Calcium Starch Octenylsuccinate; C20-40 AlkylStearate; Canolamidopropyl Betaine; Capramide DEA;Capryl/Capramidopropyl Betaine; Carbomer; Carboxybutyl Chitosan;Carboxymethyl Cellulose Acetate Butyrate; Carboxymethyl Chitin;Carboxymethyl Chitosan; Carboxymethyl Dextran; CarboxymethylHydroxyethylcellulose; Carboxymethyl Hydroxypropyl Guar; Carnitine;Cellulose Acetate Propionate Carboxylate; Cellulose Gum; CeratoniaSiliqua Gum; Cetearyl Alcohol; Cetyl Alcohol; Cetyl Babassuate; CetylBetaine; Cetyl Glycol; Cetyl Hydroxyethylcellulose; Chimyl Alcohol;Cholesterol/HDI/Pullulan Copolymer; Cholesteryl Hexyl DicarbamatePullulan; Citrus Aurantium Dulcis (Orange) Peel Extract; Cocamide DEA;Cocamide MEA; Cocamide MIPA; Cocamidoethyl Betaine; CocamidopropylBetaine; Cocamidopropyl Hydroxysultaine; Coco-Betaine;Coco-Hydroxysultaine; Coconut Alcohol; Coco/Oleamidopropyl Betaine;Coco-Sultaine; Cocoyl Sarcosinamide DEA; Cornamide/Cocamide DEA;Cornamide DEA; Croscarmellose; Crosslinked Bacillus/Glucose/SodiumGlutamate Ferment; Cyamopsis Tetragonoloba (Guar) Gum; Decyl Alcohol;Decyl Betaine; Dehydroxanthan Gum; Dextrin; Dibenzylidene Sorbitol;Diethanolaminooleamide DEA; Diglycol/CHDM/Isophthalates/SIP Copolymer;Dihydroabietyl Behenate; Dihydrogenated Tallow Benzylmonium Hectorite;Dihydroxyaluminum Aminoacetate; Dimethicone/PEG-10 Crosspolymer;Dimethicone/PEG-15 Crosspolymer; Dimethicone Propyl PG-Betaine;Dimethylacrylamide/Acrylic Acid/Polystyrene Ethyl MethacrylateCopolymer; Dimethylacrylamide/Sodium AcryloyldimethyltaurateCrosspolymer; Disteareth-100 IPDI; DMAPA Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Erucamidopropyl Hydroxysultaine;Ethylene/Sodium Acrylate Copolymer; Gelatin; Gellan Gum; GlycerylAlginate; Glycine Soja (Soybean) Flour; Guar HydroxypropyltrimoniumChloride; Hectorite; Hyaluronic Acid; Hydrated Silica; HydrogenatedPotato Starch; Hydrogenated Tallow; Hydrogenated Tallowamide DEA;Hydrogenated Tallow Betaine; Hydroxybutyl Methylcellulose; HydroxyethylAcrylate/Sodium Acryloyldimethyl Taurate Copolymer;Hydroxyethylcellulose; Hydroxyethyl Chitosan; HydroxyethylEthylcellulose; Hydroxyethyl Stearamide-MIPA;Hydroxylauryl/Hydroxymyristyl Betaine; Hydroxypropylcellulose;Hydroxypropyl Chitosan; Hydroxypropyl Ethylenediamine Carbomer;Hydroxypropyl Guar; Hydroxypropyl Methylcellulose; HydroxypropylMethylcellulose Stearoxy Ether; Hydroxypropyl Starch; HydroxypropylStarch Phosphate; Hydroxypropyl Xanthan Gum; Hydroxystearamide MEA;Isobutylene/Sodium Maleate Copolymer; Isostearamide DEA; IsostearamideMEA; Isostearamide MIPA; Isostearamidopropyl Betaine; Lactamide MEA;Lanolinamide DEA; Lauramide DEA; Lauramide MEA; Lauramide MIPA;Lauramide/Myristamide DEA; Lauramidopropyl Betaine; LauramidopropylHydroxysultaine; Laurimino Bispropanediol; Lauryl Alcohol; LaurylBetaine; Lauryl Hydroxysultaine; Lauryl/Myristyl Glycol HydroxypropylEther; Lauryl Sultaine; Lecithinamide DEA; Linoleamide DEA; LinoleamideMEA; Linoleamide MIPA; Lithium Magnesium Silicate; Lithium MagnesiumSodium Silicate; Macrocystis Pyrifera (Kelp); Magnesium Alginate;Magnesium/Aluminum/Hydroxide/Carbonate; Magnesium Aluminum Silicate;Magnesium Silicate; Magnesium Trisilicate; Methoxy PEG-22/Dodecyl GlycolCopolymer; Methylcellulose; Methyl Ethylcellulose; MethylHydroxyethylcellulose; Microcrystalline Cellulose; MilkamidopropylBetaine; Minkamide DEA; Minkamidopropyl Betaine; MIPA-Myristate;Montmorillonite; Moroccan Lava Clay; Myristamide DEA; Myristamide MEA;Myristamide MIPA; Myristamidopropyl Betaine; MyristamidopropylHydroxysultaine; Myristyl Alcohol; Myristyl Betaine; Natto Gum;Nonoxynyl Hydroxyethylcellulose; Oatamide MEA; Oatamidopropyl Betaine;Octacosanyl Glycol Isostearate; Octadecene/MA Copolymer; Oleamide DEA;Oleamide MEA; Oleamide MIPA; Oleamidopropyl Betaine; OleamidopropylHydroxysultaine; Oleyl Betaine; Olivamide DEA; Olivamidopropyl Betaine;Oliveamide MEA; Palmamide DEA; Palmamide MEA; Palmamide MIPA;Palmamidopropyl Betaine; Palmitamide DEA; Palmitamide MEA;Palmitamidopropyl Betaine; Palm Kernel Alcohol; Palm Kernelamide DEA;Palm Kernelamide MEA; Palm Kernelamide MIPA; Palm KernelamidopropylBetaine; Peanutamide MEA; Peanutamide MIPA; Pectin; PEG-800;PEG-Crosspolymer; PEG-150/Decyl Alcohol/SMDI Copolymer; PEG-175Diisostearate; PEG-190 Distearate; PEG-15 Glyceryl Tristearate; PEG-140Glyceryl Tristearate; PEG-240/HDI Copolymer Bis-Decyltetradeceth-20Ether; PEG-100/IPDI Copolymer; PEG-180/Laureth-50/TMMG Copolymer;PEG-10/Lauryl Dimethicone Crosspolymer; PEG-15/Lauryl DimethiconeCrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 Methyl Glucose Trioleate; PEG-180/Octoxynol-40/TMMG Copolymer;PEG-150 Pentaerythrityl Tetrastearate; PEG-4 Rapeseedamide;PEG-150/Stearyl Alcohol/SMDI Copolymer; Phaseolus Angularis Seed Powder;Polianthes Tuberosa Extract; Polyacrylate-3; Polyacrylic Acid;Polycyclopentadiene; Polyether-1; Polyethylene/Isopropyl Maleate/MACopolyol; Polyglyceryl-3 Disiloxane Dimethicone; Polyglyceryl-3Polydimethylsiloxyethyl Dimethicone; Polymethacrylic Acid;Polyquaternium-52; Polyvinyl Alcohol; Potassium Alginate; PotassiumAluminum Polyacrylate; Potassium Carbomer; Potassium Carrageenan;Potassium Chloride; Potassium Palmate; Potassium Polyacrylate; PotassiumSulfate; Potato Starch Modified; PPG-2 Cocamide; PPG-1 HydroxyethylCaprylamide; PPG-2 Hydroxyethyl Cocamide; PPG-2 HydroxyethylCoco/Isostearamide; PPG-3 Hydroxyethyl Soyamide; PPG-14 Laureth-60 HexylDicarbamate; PPG-14 Laureth-60 Isophoryl Dicarbamate; PPG-14 Palmeth-60Hexyl Dicarbamate; Propylene Glycol Alginate; PVP/Decene Copolymer; PVPMontmorillonite; Pyrus Cydonia Seed; Pyrus Malus (Apple) Fiber;Rhizobian Gum; Ricebranamide DEA; Ricinoleamide DEA; Ricinoleamide MEA;Ricinoleamide MIPA; Ricinoleamidopropyl Betaine; Ricinoleic Acid/AdipicAcid/AEEA Copolymer; Rosa Multiflora Flower Wax; Sclerotium Gum;Sesamide DEA; Sesamidopropyl Betaine; Sodium Acrylate/AcryloyldimethylTaurate Copolymer; Sodium Acrylates/Acrolein Copolymer; SodiumAcrylates/Acrylonitrogens Copolymer; Sodium Acrylates Copolymer; SodiumAcrylates Crosspolymer; Sodium Acrylate/Sodium AcrylamidomethylpropaneSulfonate Copolymer; Sodium AcrylatesNinyl Isodecanoate Crosspolymer;Sodium Acrylate/Vinyl Alcohol Copolymer; Sodium Carbomer; SodiumCarboxymethyl Chitin; Sodium Carboxymethyl Dextran; Sodium CarboxymethylBeta-Glucan; Sodium Carboxymethyl Starch; Sodium Carrageenan; SodiumCellulose Sulfate; Sodium Chloride; Sodium Cyclodextrin Sulfate; SodiumHydroxypropyl Starch Phosphate; Sodium Isooctylene/MA Copolymer; SodiumMagnesium Fluorosilicate; Sodium Oleate; Sodium Palmitate; Sodium PalmKernelate; Sodium Polyacrylate; Sodium Polyacrylate Starch; SodiumPolyacryloyldimethyl Taurate; Sodium Polygamma-Glutamate; SodiumPolymethacrylate; Sodium Polystyrene Sulfonate; Sodium Silicoaluminate;Sodium Starch Octenylsuccinate; Sodium Stearate; Sodium StearoxyPG-Hydroxyethylcellulose Sulfonate; Sodium Styrene/Acrylates Copolymer;Sodium Sulfate; Sodium Tallowate; Sodium Tauride Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Sodium Tocopheryl Phosphate; SolanumTuberosum (Potato) Starch; Soyamide DEA; Soyamidopropyl Betaine;Starch/Acrylates/Acrylamide Copolymer; Starch HydroxypropyltrimoniumChloride; Stearamide AMP; Stearamide DEA; Stearamide DEA-Distearate;Stearamide DIBA-Stearate; Stearamide MEA; Stearamide MEA-Stearate;Stearamide MIPA; Stearamidopropyl Betaine; Steareth-60 Cetyl Ether;Steareth-100/PEG-136/HDI Copolymer; Stearyl Alcohol; Stearyl Betaine;Sterculia Urens Gum; Synthetic Fluorphlogopite; Tallamide DEA; TallowAlcohol; Tallowamide DEA; Tallowamide MEA; Tallowamidopropyl Betaine;Tallowamidopropyl Hydroxysultaine; Tallowamine Oxide; Tallow Betaine;Tallow Dihydroxyethyl Betaine; Tamarindus Indica Seed Gum; TapiocaStarch; TEA-Alginate; TEA-Carbomer; TEA-Hydrochloride; Trideceth-2Carboxamide MEA; Tridecyl Alcohol; Triethylene Glycol Dibenzoate;Trimethyl Pentanol Hydroxyethyl Ether; Triticum Vulgare (Wheat) GermPowder; Triticum Vulgare (Wheat) Kernel Flour; Triticum Vulgare (Wheat)Starch; Tromethamine Acrylates/Acrylonitrogens Copolymer; TromethamineMagnesium Aluminum Silicate; Undecyl Alcohol; Undecylenamide DEA;Undecylenamide MEA; Undecylenamidopropyl Betaine; Welan Gum; WheatGermamide DEA; Wheat Germamidopropyl Betaine; Xanthan Gum; YeastBeta-Glucan; Yeast Polysaccharides and Zea Mays (Corn) Starch.

In one such embodiment, the thickeners or viscosity increasing agentsinclude carbomers, Aculyn™ and Stabileze®, e.g., crosslinked acrylicacid, crosslinked poly(methylvinyl ether/maleic anhydride) copolymer,acrylamides, carboxymethyl cellulose, and the like.

The personal care/cosmetic compositions may be used to wash and treatkeratinous material such as hair, skin, eyelashes, eyebrows,fingernails, lips, and hairy skin.

The personal care/cosmetic compositions can be detergent compositionssuch as shampoos, bath gels, and bubble baths. In this mode, thecompositions will comprise a generally aqueous washing base. Thesurfactant or surfactants that form the washing base may be chosen aloneor in blends, from known anionic, amphoteric, or non-ionic surfactants.The quantity and quality of the washing base must be sufficient toimpart a satisfactory foaming and/or detergent value to the finalcomposition. The washing base can be from about 4% to about 50% byweight, particularly from about 6% to about 35% by weight, and even moreparticularly from about 8% to about 25% by weight of the total weight ofthe final composition.

The pH of the composition applied to the keratinous material isgenerally between 2 and 12. In one embodiment, the pH is from about 3 toabout 8, and may be adjusted to the desired value by means of acidifyingor alkalinizing agents that are well known in the state of the art.Thus, the composition of the invention can contain at least onealkalizing or acidifying agent in amounts from about 0.01% to about 30%based on the total weight of the composition.

The alkalizing agent can be chosen from ammonia, alkali carbonates,alkanolamines, like mono-, di- and triethanolamines, as well as theirderivatives, hydroxyalkylamines and ethoxylated and/or propoxylatedethylenediamines, sodium or potassium hydroxides and compounds of thefollowing formula:

in which R is a propylene residue optionally substituted with anhydroxyl group or a C₁-C₄ alkyl radical; R₃₈, R₃₉, R₄₀ and R₄₁,identical or different, represent a hydrogen atom, a C₁-C₄ alkyl radicalor C₁-C₄ hydroxyalkyl radical.

The acidifying agent can be chosen from mineral or organic acids, likehydrochloric acid, orthophosphoric acid, carboxylic acids like tartaricacid, citric acid, or lactic acid, or sulfonic acids, and the like.

The personal care/cosmetic compositions of the invention may include aphysiological and cosmetically acceptable medium. Such medium mayconsist exclusively of water, a cosmetically acceptable solvent, or ablend of water and a cosmetically acceptable solvent, such as a loweralcohol composed of C₁ to C₄, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.Alternatively, the personal care/cosmetic compositions can be anhydrous.

Generally, personal care/cosmetic compositions can be prepared by simplemixing procedures well known in the art. The invention provides a methodfor treating keratinous material including the skin or hair, by applyingto skin or keratinous materials a personal care/cosmetic composition asdescribed above, and then eventually rinsing it with water. Accordingly,the method makes it possible to maintain the hairstyle, treatment, care,washing, or make-up removal of the skin, the hair, and any otherkeratinous material. The personal care/cosmetic compositions may alsotake the form of after-shampoo compositions, to be rinsed off or not,for permanents, straightening, waving, dyeing, or bleaching, or the formof rinse compositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process. The personalcare/cosmetic compositions may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products. The personalcare/cosmetic compositions may also be in the form of aqueous orhydro-alcoholic solutions for skin and/or hair care. The personalcare/cosmetic compositions described herein are useful in personalcare/cosmetic products, including, but not limited to, gels, lotions,glazes, glues, mousses, sprays, fixatives, shampoos, conditioners,2-in-1 shampoos, temporary hair dyes, semi-permanent hair dyes,permanent hair dyes, straighteners, permanent waves, relaxers, creams,putties, waxes, pomades, moisturizers, mascaras, lip balms and foamenhancers.

The modified polymers can be prepared according to the examples set outbelow. The examples are presented for purposes of demonstrating, but notlimiting, the preparation of the compounds and compositions of thisinvention.

EXAMPLES

The following non-limiting examples are provided to illustrate a few ofthe methods for preparing novel containing an acetoacetate moiety andfunctionalized polymers. The examples are presented for purposes ofdemonstrating, but not limiting, the preparation of the compounds andcompositions of this invention.

Example 1

Feed 1 was prepared with 37.62 g of phenoxyethyl acrylate (PEA), 37.62 gof methyl ethyl ketone (MEK), 19.18 g of maleic anhydride (MAN), and41.91 g of acetoacetoxyethyl methacrylate (AAEM, AcAc). 180.58 g of MEKwere placed into a reaction flask and the reaction flask was purged withnitrogen. The reaction flask containing MEK was heated to reflux, ˜78°C. In a separate reaction flask, a mixture of Triganox 25C 75 (15.0 g)and MEK (15 g) was prepared. This reaction flask was labeled “TriganoxSolution”. When the MEK reaction flask reached reflux temperature, Feed1 was added drop-wise over a period of about 180 minutes. After 15minutes of monomer feed, 3 g of the Triganox Solution was added into thereaction flask and the drop-wise addition of Feed 1 was continued over aperiod of about 165 minutes. After 30 minutes into the monomers beingfeed into the reaction flask, 3.0 g of the Triganox solution was added.After 45, 60, 75, 90, 105, 120, and 150 minutes, 3.0 g Triganox solutionwas added into the reaction flask. At the completion of the monomerfeeds, the remainder of the Triganox solution was added to the reactionflask. The reaction flask was heated at reflux for an additional 180minutes. During the additions, additional MEK was added to replace anythat volatilized. The reaction flask was cooled; this was the end of“day one”. On “day two”, the contents in the reaction flask were heatedto reflux and charged with 2.0 g Triganox 25C 75 and maintained atreflux for 2 hours. An additional 2.0 g of Triganox 25C 75 was added atreflux for 5 hours and then the reaction mixture was cooled.

Monomer Mass (grams) Moles PEA 37.62 0.196 MAN 19.18 0.196 AAEM 41.910.196

Example 2

Using the procedure set out in Example 1, the compound illustrated abovewas prepared, using Ebecryl IBOA (IBOA,(1S,4S)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl]prop-2-enoate) andallyl acetoacetate (prop-2-enyl 3-oxobutanoate).

Monomer Mass (grams) Moles IBOA 42.06 0.202 MAN 19.8 0.202 Allylacetoacetate 28.71 0.202

Example 3

Using the procedure set out in Example 1, the compound illustrated abovewas prepared.

Monomer Mass (grams) Moles PEA 8.66 0.045 AAEM 86.92 0.406

Example 4

Using the procedure set out in Example 1, the compound illustrated abovewas prepared, using lauryl methacrylate (LM, 2-propenoic acid,2-methyl-, dodecyl ester).

Monomer Mass (grams) Moles LM 61.6 0.24 PEA 46.5 0.24 AAEM 11.5 0.05

Example 5

Using the procedure set out in Example 1, the compound illustrated abovewas prepared.

Monomer Mass (grams) Moles IBOA 75 0.36 AAEM 8.6 0.04

Example 6

Using the procedure set out in Example 1, the compound illustrated abovewas prepared, using ODA (octyl/decyl acrylate).

Monomer Mass (grams) Moles IBOA 29.16 0.14 ODA 28.42 0.14 AAEM 25.710.12

Example 7

Using the procedure set out in Example 1, the compound illustrated abovewas prepared, using ODA (octyl/decyl acrylate).

Monomer Mass (grams) Moles PEA 48.2 0.251 ODA 51.0 0.251 AAEM 11.9 0.06

While a number of embodiments of this invention have been represented,it was apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

We claim:
 1. A polymer containing an acetoacetate moiety having thefollowing structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent.
 2. The polymer according to claim 1, wherein each R₁ and R₂ areindependently hydrogen or methyl.
 3. The polymer according to claim 1,wherein —R₃— is —C(O)OCH₂CH₂—.
 4. The polymer according to claim 1,wherein each R₄ is independently selected from the group consisting offunctionalized and unfunctionalized alkoxy, amide, aryl, carbonyl,carboxyl, cycloalkyl groups, and moieties derived from triethoxyvinylsilane, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof.
 5. The polymer according toclaim 1, wherein each R₅ is independently selected from the groupconsisting of C₁-C₈ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof.
 6. The polymer accordingto claim 1, wherein x ranges from 1-98%, y ranges from 1-98%, and wranges from 0-98%.
 7. The polymer according to claim 1, wherein thepolymer has a structure selected from the group consisting of:


8. A polymer containing an acetoacetate moiety having the followingstructure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; y and z are mole percent,the sum of which=100%.
 9. The polymer according to claim 8, wherein eachR₁ and R₂ are independently hydrogen or methyl.
 10. The polymeraccording to claim 8, wherein —R₃— is —C(O)OCH₂CH₂—.
 11. The polymeraccording to claim 8, wherein each R₄ is independently selected from thegroup consisting of functionalized and unfunctionalized alkoxy, amide,aryl, carbonyl, carboxyl, cycloalkyl groups, and moieties derived fromtriethoxyvinyl silane, wherein any of the before mentioned groups may bewith or without heteroatoms, and mixtures thereof.
 12. The polymeraccording to claim 8, wherein each R₅ is independently selected from thegroup consisting of C₁-C₈ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof.
 13. The polymer accordingto claim 8, wherein y ranges from 1-99% and z ranges from 1-99%.
 14. Thepolymer according to claim 8, wherein the polymer has a structureselected from the group consisting of:


15. A composition comprising a polymer containing an acetoacetate moietyhaving the following structure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; w, y, and z are molepercent, the sum of which=100%, with the proviso that z may be 0% molepercent.
 16. The composition according to claim 15, wherein each R₁ andR₂ are independently hydrogen or methyl.
 17. The composition accordingto claim 15, wherein —R₃— is —C(O)OCH₂CH₂—.
 18. The compositionaccording to claim 15, wherein each R₄ is independently selected fromthe group consisting of functionalized and unfunctionalized alkoxy,amide, aryl, carbonyl, carboxyl, cycloalkyl groups, and moieties derivedfrom triethoxyvinyl silane, wherein any of the before mentioned groupsmay be with or without heteroatoms, and mixtures thereof.
 19. Thecomposition according to claim 15, wherein each R₅ is independentlyselected from the group consisting of C₁-C₈ functionalized andunfunctionalized alkyl and alkenyl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof.
 20. The composition according to claim 15, wherein x rangesfrom 1-98%, y ranges from 1-98%, and w ranges from 0-98%.
 21. Thecomposition according to claim 15, wherein the polymer has a structureselected from the group consisting of:


22. A composition containing an acetoacetate moiety having the followingstructure:

wherein R₁ and R₂ are each independently selected from the groupconsisting of hydrogen and C₁-C₃₀ functionalized and unfunctionalizedalkyl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; each R₃ is independentlyselected from the group consisting of hydrogen and C₁-C₆ functionalizedand unfunctionalized alkyl, amide, carbonyl, and carboxyl groups,wherein any of the before mentioned groups may be with or withoutheteroatoms, and mixtures thereof; each R₄ is independently selectedfrom the group consisting of functionalized and unfunctionalizedalkenyl, alkoxy, alkyl, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from trialkoxyvinyl silanes, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof; each R₅ is independently selected from the groupconsisting of C₁-C₁₂ functionalized and unfunctionalized alkyl andalkenyl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof; y and z are mole percent,the sum of which=100%.
 23. The composition according to claim 22,wherein each R₁ and R₂ are independently hydrogen or methyl.
 24. Thecomposition according to claim 22, wherein —R₃— is —C(O)OCH₂CH₂—. 25.The composition according to claim 22, wherein each R₄ is independentlyselected from the group consisting of functionalized andunfunctionalized alkoxy, amide, aryl, carbonyl, carboxyl, cycloalkylgroups, and moieties derived from triethoxyvinyl silane, wherein any ofthe before mentioned groups may be with or without heteroatoms, andmixtures thereof.
 26. The composition according to claim 22, whereineach R₅ is independently selected from the group consisting of C₁-C₈functionalized and unfunctionalized alkyl and alkenyl groups, whereinany of the before mentioned groups may be with or without heteroatoms,and mixtures thereof.
 27. The composition according to claim 22, whereiny ranges from 1-99% and z ranges from 1-99%.
 28. The compositionaccording to claim 22, wherein the polymer has a structure selected fromthe group consisting of:


29. The composition according to claim 15, wherein the compositioncomprises adhesives, aerosols, agricultural compositions, anti-soilredeposition agents, batteries, beverages, biocides, block copolymers,branch/comb copolymers, cementing compositions, cleaning compositions,coating compositions, conductive materials, cosmetic compositions,cross-linkers, dental compositions, decorated pigments, detergents,dispersants, drugs, electronics, encapsulations, foods, hair sprays,household-industrial-institutional, inks and coatings, interlaminateadhesives, lithographic solutions, membrane additive compositions, metalworking fluids, oilfield compositions, paints, paper, personal carecompositions, pharmaceuticals, pigment additives, plasters, plastics,printing, reactive biocides, refractive index modifiers, sequestrants,soil release compositions, static control agents, and wood-carecompositions.
 30. The composition according to claim 22, wherein thecomposition comprises adhesives, aerosols, agricultural compositions,anti-soil redeposition agents, batteries, beverages, biocides, blockcopolymers, branch/comb copolymers, cementing compositions, cleaningcompositions, coating compositions, conductive materials, cosmeticcompositions, cross-linkers, decorated pigments, dental compositions,detergents, dispersants, drugs, electronics, encapsulations, foods, hairsprays, household-industrial-institutional, inks and coatings,interlaminate adhesives, lithographic solutions, membrane additivecompositions, metal working fluids, oilfield compositions, paints,paper, personal care compositions, pharmaceuticals, pigment additives,plasters, plastics, printing, reactive biocides, refractive indexmodifiers, sequestrants, soil release compositions, static controlagents, and wood-care compositions.